Conjugated porous polymers (CPPs) incorporating donor–acceptor (D–A) structures are gaining significant interest for their potential in photocatalytic hydrogen evolution reaction (HER). The microstructure and electronic properties of the polymer frameworks are crucial for optimizing their photocatalytic efficiency. Here, we design two D–A type CPP photocatalysts using 4,8-di(thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene (DBD) and triazine units to investigate the impact of different bridging units on HER activity. Compared with PhDBD–CPP using benzene as the bridging unit, ThDBD–CPP with a thiophene linking unit achieves an expansion of the HOMO orbital distribution and an enlarged molecular dipole moment, which is conducive to the efficient separation and migration of photogenerated carriers. Consequently, ThDBD–CPP with thiophene as the bridging unit exhibits a remarkable photocatalytic hydrogen evolution rate of 20.75 mmol h⁻¹ g⁻¹ under full arc light. After loading 1 wt% Pt cocatalyst, the HER activity is further improved to 30.36 mmol h⁻¹ g⁻¹. This study suggests that modulating bridging units provides a new viable approach to designing efficient polymer photocatalysts.

中文翻译：

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基于三嗪和多支化多环噻吩的交联共轭聚合物可改善光催化析氢


结合供体-受体（D-A）结构的共轭多孔聚合物（CPP）因其在光催化析氢反应（HER）中的潜力而引起人们极大的兴趣。聚合物框架的微观结构和电子性能对于优化其光催化效率至关重要。在这里，我们使用 4,8-二(噻吩-2-基)苯并[1,2- b :4,5- b ']二噻吩 (DBD) 和三嗪单元设计了两种 D-A 型 CPP 光催化剂，以研究其影响不同桥接单元对 HER 活性的影响。与以苯为桥联单元的PhDBD-CPP相比，带有噻吩连接单元的ThDBD-CPP实现了HOMO轨道分布的扩展和分子偶极矩的扩大，有利于光生载流子的高效分离和迁移。因此，以噻吩为桥联单元的ThDBD-CPP在全弧光下表现出20.75 mmol h ^-1 g ^-1的显着光催化析氢速率。负载1 wt% Pt助催化剂后，HER活性进一步提高至30.36 mmol h ^-1 g ^-1 。这项研究表明，调节桥接单元为设计高效聚合物光催化剂提供了一种新的可行方法。